Abstract
A new stable radical‐containing ligand and the corresponding VV, TiIV, and MoVI complexes have been synthesized and studied by electron paramagnetic resonance (EPR) spectroscopy. To achieve this goal, a novel strategy for the post‐derivatization of a triphenolamine (TPA) ligand has been developed. This has allowed the effective embedding of three TEMPO (2,2,6,6‐tetramethyl‐1‐piperidinyloxy) radicals in the corresponding metal complexes. In these systems, dipolar interactions among the organic radicals are strongly dependent on the geometry assumed in solution: a |Δms| = 2 transition is observed when the geometry of the complexes is octahedral, whereas no signal is detected with trigonal bipyramidal geometries.
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